CN106582269A - Method for catalyzing ethane oxidation by using modified iron catalyst - Google Patents
Method for catalyzing ethane oxidation by using modified iron catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Abstract
The invention belongs to the field of industrial catalysis and environmental protection, and provides a method for catalyzing ethane oxidation by using a modified iron catalyst. The method comprises three parts including preparation of the modified iron catalyst, preparation of a reaction system for catalyzing ethane oxidation by using the modified iron catalyst, and control of a reaction condition for ethane catalytic oxidation, wherein the preparation process of the modified iron catalyst comprises the following steps: 1, preparing raw materials; 2, performing soaking in a first mixed solution, 3, performing base catalysis hydrolysis; 4, performing catalyst roasting; and 5, performing loop operation for multiple times. During the preparation of the reaction system for catalyzing ethane oxidation by using the modified iron catalyst, an ethane oxidation fixed bed reaction device is used. By control of the reaction condition for ethane catalytic oxidation, the conversion rate of ethane can reach 90% or above. For ethane oxidation, compared with an unmodified iron catalyst, the modified iron catalyst can obtain an obviously improved ethane conversion rate and an obviously improved yield of a complete oxidation product namely carbon dioxide.
Description
Technical field
The invention belongs to Industrial Catalysis and field of environment protection, are related to a kind of method of ethane oxidation；In particular it relates to
A kind of method using modification sections catalyst ethane oxidation, the preparation method comprising catalyst, and catalytic reaction mistake
Process control method.
Background technology
Small molecule alkane, such as methane, ethane, propane etc. are the gas of the strong greenhouse effect of a class.The greenhouse effect of such as methane
It should be 25 times of carbon dioxide or so.The discharge of small molecule alkane will cause larger atmospheric pollution.Small molecule alkane is due to which
Chemical constitution saturability, chemical property torpescence, carries out the chemical conversion generally higher cost of needs to which under normal circumstances.From
Say on principles of chemical kinetics, the chemical conversion of small molecule alkane generally needs larger activation energy.Therefore will be in temperate condition
Under, lead to snperoxiaized method and remove small molecule alkane, need the catalyst of high catalytic activity.Loaded catalyst is industrial Jing
A kind of catalyst type for often using.
Due to elemental iron widely distributed property with it is cheap, ferrum usually is paid the utmost attention to be used as by Industrial Catalysis art personnel
Catalytically-active metals component, or one of which active component.Due to the general activity of catalyst it is closely related with preparation means, because
The new method for preparing catalyst of this exploitation is one lasting Scientific And Technical Problems of catalytic field technical staff.It is catalyzed with regard to loading type iron
The preparation of agent is very more with the report of catalytic performance, but for the method for modifying of loaded catalyst, and the effect after modification
Fruit research is considerably less.
Patent CN1431048A describes a kind of preparation method of load typed iron catalyst and which possesses oxidation of alkanes
Effect.The presoma of the presoma and auxiliary agent of Fe components is made into its inventor solution that concentration is 0.1～6mol/L respectively, is pressed
Ratio is by activated carbon or γ-Al2O3It is impregnated in the solution of Fe presomas and auxiliary agent presoma, after dipping, stands 18～36 hours,
110～120 DEG C of dryings 4～6 hours, under nitrogen protection in 450～650 DEG C, roasting 4～5 hours enters exsiccator.The invention
Preparation process comprise only the load of ferrous metal component, without comprising follow-up modification process.Catalyst is in actual alkane oxygen
During change, temperature is higher, and active component is in constantly oxidation and reduces in circulation, causes active component easily existing in catalysis
Field aggregation, makes catalysis activity substantially reduce even inactivation.
Document [Luyao Xu et al., Alumina-supported Fe catalyst prepared by vapor
deposition and its catalytic performance for oxidative dehydrogenation of
Ethane, Materials Research Bulletin, 59 (2014) 254-260.] report a kind of loading type iron and urge
The gas-phase deposition process for preparing of agent.The method read fortune from principle can improve ferrum component for traditional methods such as infusion processes
Degree of scatter, is expected to have the improvement on catalytic performance for reactions such as catalysis oxidation of alkanes.The document is found for ethane oxidation
For, the catalyst of the identical iron content that iron catalyst prepared by vapour deposition process is prepared with infusion process, its catalyzed conversion activity
Improve about 4 times.But the document is not still contained for the report of modification process after the load of ferrum component.
In sum, also there is the technical need of further Development of Novel iron catalyst method of modifying in this area, and need
Its application prospect in oxidation of alkanes is explored further.
The content of the invention
In the presence of overcoming the shortcomings of prior art, the present invention provides a kind of using modification sections catalyst second
The method of alkoxide.Technical scheme makes every effort to avoid using noxious substance and expensive device, so that whole technique side
Method is low cost, operated, eco-friendly method.
The present invention adopts following proposal：
A kind of method using modification sections catalyst ethane oxidation, including the preparation of modification sections catalyst, modification type
The reaction system of iron catalyst catalysis ethane oxidation prepares, and the reaction condition of ethane catalysis oxidation controls three parts.Its
The preparation process of middle modification iron catalyst includes following step：
Step one, raw material prepare；
Step 2, the first mixed liquid dipping；
Step 3, alkali catalyzed hydrolysiss；
Step 4, catalyst roasting；
Step 5, multiple circulate operation；
The reaction system of modification sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor, including：
Main reactor tube, main reactor tube have main reactor tube air inlet, main reactor tube gas outlet；Oxygen source, there is provided purity oxygen；Ethane gas
Source, there is provided pure ethane gas；Noble gas source, there is provided N2The mixing of one or more gases in gas, He gas, Ar gas
Thing；Oxygen source, ethane source of the gas, the flow of noble gas source pass through first flow controller, second flow controller respectively
Control with the 3rd flow controller；Oxygen source is after first flow controller, ethane source of the gas is controlled by second flow
After device, noble gas source be merged into after the 3rd flow controller all the way, become the unstripped gas of ethane oxidation；Flow of feed gas
Enter main reactor tube air inlet, flow out from main reactor tube gas outlet；Catalyst can be filled in beds are formed in main reactor tube；
All gases for flowing through beds are final all to flow out from main reactor tube gas outlet, forms product gas.
Above-mentioned " modification sections catalyst " is filled in beds are formed in main reactor tube, beds are full of master
The section of reaction tube.
The reaction condition control of ethane catalysis oxidation, concrete grammar are as follows：
Open oxygen source, ethane source of the gas and noble gas source, and by first flow controller, second flow controller and
3rd flow controller controls the flow velocity of oxygen, ethane and noble gases respectively；The temperature of control beds.When all of
When the temperature of gas flow rate and beds reaches setting value, the reaction condition control of ethane oxidation is finished, and is started continuous raw
Produce.
Using the method for above-mentioned modification sections catalyst ethane oxidation, the present invention is it was discovered by researchers that ethane turns
Rate can be more than 85%.
Beneficial effects of the present invention are as follows：
(1), for load typed iron catalyst, the invention provides modifying the preparation of sections catalyst and being used for ethane oxygen
The whole set process flow process of change, gives more considerable ethane conversion under the conditions of relatively mild.
(2), show with comparative example result in conjunction with the embodiments, for ethane oxidation, modify sections catalyst and do not repair
The iron catalyst of decorations is compared, and may be significantly the yield of the ethane conversion and complete oxidation product carbon dioxide of raising.
(3) each step operation of the invention is fairly simple, and involved equipment belongs to conventional equipment, involved each thing
Matter belongs to environmental friendliness material, and operation and the environmentally friendly cost for implementing the present invention is relatively low, while safe operation, personnel protection cost
It is relatively low, it is suitable for large-scale production and industrial applications.
Description of the drawings
Fig. 1 is ethane oxidation fixed-bed reactor structural representation.
In figure, 1, main reactor tube；2nd, main reactor tube air inlet；3rd, main reactor tube gas outlet；4th, oxygen source；5th, ethane gas
Source；6th, noble gas source；7th, first flow controller；8th, second flow controller；9th, the 3rd flow controller；10th, raw material
Gas；11st, product gas；12nd, beds；Thick-line arrow represents the flow direction of gas.
Specific embodiment
A kind of method using modification sections catalyst ethane oxidation, including the preparation of modification sections catalyst, repair
The reaction system of decorations sections catalyst ethane oxidation prepares, and the reaction condition of ethane catalysis oxidation controls three portions
Point.The preparation process for wherein modifying iron catalyst includes following step：
Step one, raw material prepare；Including following raw material：
Initial load sections catalyst, containing catalyst carrier and active metal component；The chemical composition of catalyst carrier is oxygen
Change aluminum；Active metal component is ferrum or iron oxides；In initial load sections catalyst, the load capacity of ferrum is 0.5 ~ 10
wt%；The specific surface area of initial load sections catalyst is more than 100 m2/g；Initial load sections catalyst be graininess, granule
Magnitude range is within 10 ~ 200 mesh；
First mixed liquor, its concrete compound method are by alcohol and two class material mixing of positive esters of silicon acis, before the quality of latter of which is
0.2 ~ 15 times of person；Wherein positive esters of silicon acis refer to methyl silicate, tetraethyl orthosilicate, one in positive silicic acid propyl ester three,
Or their arbitrary proportion mixture；Wherein alcohol refers in methanol, ethanol, 1- propanol, 2- propanol, or they
Arbitrary proportion mixture；Obtained mixed liquor is referred to as the first mixed liquor；
Ammonia, refers to containing NH3Aqueous solution of the mass percent more than 3%；
First roasting source of the gas, refers specifically to compressed air, oxygen, nitrogen, argon, helium, or above-mentioned these gases are any
Ratio gaseous mixture.
Step 2, the first mixed liquid dipping；Concrete grammar is as follows：
Initial load sections catalyst described in step one is completely soaked in the first mixed liquor；The time is completely soaked for 20
min ~ 48 h；After immersion is completed, the first unnecessary mixed liquor is filtered out, load typed iron catalyst granule is left.
Step 3, alkali catalyzed hydrolysiss；Concrete grammar is as follows：
Prepare two containers, be referred to as the first container and second container；First container is an open container；Second container
For a hermetic container with cover, whole first container under air-tight state, can be held；Under second container opening-wide state, it is put into
A certain amount of ammonia, its quality are 5 ~ 1000 times of initial load sections catalyst quality；To complete negative obtained by step 2
Carry sections catalyst to be put in the first container, and the first container is put into into second container；Wherein ammonia and the first container are put into
The time sequencing of two containers is random order；Hermetic container will be formed on the lid lid of second container；After closeing the lid, keep 4 ~
48h；Take out the load typed iron catalyst in the first container.
Step 4, catalyst roasting；Concrete grammar is as follows：
Load typed iron catalyst obtained by step 3 is processed is exposed in atmosphere, or is exposed to the first roasting source of the gas
Roasting under the atmosphere for being formed；Roasting time is 30 min ~ 24 h, and sintering temperature is 200 ~ 750oC。
Step 5, multiple circulate operation；Concrete grammar is as follows：
Using the load typed iron catalyst completed obtained by the step 4, " original negative described in alternative steps one " raw material preparation "
Carry sections catalyst " raw material, carry out new one cycle operation；Wherein step one is referred to step 4 per " one cycle operation "
Described all operationss；The total degree that circulate operation is performed is 1 ~ 15 time.
In step 5, involved liquid composition in arbitrarily once new circulate operation, gas composition, sintering temperature,
The operating parameters such as roasting time, soak time, can be identical with the parameter of its front circulate operation, it is also possible to different；Parameter
Select in above-mentioned steps one to the scope described by step 4.
" specific surface area " described in above-mentioned steps one is a term in catalyst and surface chemistry field, is referred to
The microcosmic surface product that the catalyst of unit mass has.In the art, a most frequently used assay method of specific surface area is
Brunauer-Emmett-Teller (BET) method, by determining N under low temperature2Adsorption desorption curve on a catalyst is calculated
Arrive.What " specific surface area " carried in the present invention referred to is also to determine the numerical value for obtaining by BET methods.
" being completely soaked " in above-mentioned steps two, refers to from timing start to timing in all times for terminating, solid
Granule is immersed in liquid all the time.
" initial load sections catalysis after above-mentioned steps one to step 5, described in step one " raw material preparation "
Agent " is turned into " modification sections catalyst ".
The reaction system of modification sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor,
As shown in figure 1, including：Main reactor tube 1, main reactor tube 1 have main reactor tube air inlet 2, main reactor tube gas outlet 3；Oxygen gas
Source 4, there is provided purity oxygen；Ethane source of the gas 5, there is provided pure ethane gas；Noble gas source 6, there is provided N2In gas, He gas, Ar gas
The mixture of one or more gases；Oxygen source 4, ethane source of the gas 5, the flow of noble gas source 6 pass through first respectively
Flow controller 7, second flow controller 8 and the 3rd flow controller 9 are controlling；Oxygen source 4 is controlled by first flow
After device 7, ethane source of the gas 5 by after second flow controller 8, noble gas source 6 is by being merged into after the 3rd flow controller 9
All the way, become the unstripped gas 10 of ethane oxidation；Unstripped gas 10 flows into main reactor tube air inlet 2, flows from main reactor tube gas outlet 3
Go out；Catalyst can be filled in beds 12 are formed in main reactor tube 1；All gases for flowing through beds 12 are final all
Flow out from main reactor tube gas outlet 3, form product gas 11.
Above-mentioned " modification sections catalyst " is filled in beds 12, beds 12 are formed in main reactor tube 1
Section full of main reactor tube 1；The modification sections catalyst gross mass of filling is designated as mcat。
The reaction condition control of ethane catalysis oxidation, concrete grammar are as follows：
Oxygen source 4, ethane source of the gas 5 and noble gas source 6 are opened, and is controlled by first flow controller 7, second flow
Device 8 and the 3rd flow controller 9 control the flow velocity of oxygen, ethane and noble gases respectively；The mass velocity of ethane is designated as into F
(C2H6), the mass velocity of oxygen is designated as F (O2), the mass velocity of noble gases is designated as F (Inert)；Control F (C2H6) 0.07
~3 mcat*h-1In the range of；Control F (O2) for F (C2H6) 2 ~ 8 times；Control F (Inert) is F (C2H6) 1 ~ 50 times；Control
The temperature of beds processed 12 is 300 ~ 750oA desired value between C.
Above-mentioned " mass velocity " refers to the gaseous mass for flowing through any one flow controller per hour.
When the temperature of all of gas flow rate and beds 12 reaches setting value, the reaction bar of ethane catalysis oxidation
Part control is finished, and starts continuous production.
Technical staff after continuous production starts can be sampled to product gas 11 and quantitative analyses, calculates ethane
Conversion ratio and yield of carbon dioxide.For using the reaction-ure conversion-age of catalytic reaction in fixed bed reactors, object yield,
Object is selectively measured and is calculated, and is a routine operation content of catalytic field, not within protection scope of the present invention.
In this area, a way for being easier to realize is to analyze the unstripped gas 10 of ethane oxidation respectively by on-line gas chromatography
And the gas composition of product gas 11, and ethane conversion is calculated by following formula（XC2%）With the yield of carbon dioxide (Y%)：
,
；
Wherein [C 2 H 6]0The concentration of ethane and oxygen in unstripped gas 10 is represented respectively；[C 2 H 6]1[CO 2]1Represent respectively ethane and
Concentration of the carbon dioxide in product gas 11.
Using the method for above-mentioned modification sections catalyst ethane oxidation, the present invention is it was discovered by researchers that ethane turns
Rate can be more than 85%.
Embodiment one,
A kind of method using modification sections catalyst ethane oxidation, including the preparation of modification sections catalyst, modification type
The reaction system of iron catalyst catalysis ethane oxidation prepares, and the reaction condition of ethane catalysis oxidation controls three parts.Its
The preparation process of middle modification iron catalyst includes following step：
Step one, raw material prepare；Including following raw material：
Initial load sections catalyst, containing catalyst carrier and active metal component；The chemical composition of catalyst carrier is oxygen
Change aluminum；Active metal component is ferrum or iron oxides；In initial load sections catalyst, the load capacity of ferrum is 3.5 wt%；Just
The specific surface area of beginning load typed iron catalyst is 260 m2/g；Initial load sections catalyst be graininess, granular size scope
Between 20 ~ 40 mesh；Initial load sections catalyst gross mass is 4.0 g；
First mixed liquor, its concrete compound method are by alcohol and two class material mixing of positive esters of silicon acis, before the quality of latter of which is
0.7 times of person；Wherein positive esters of silicon acis refers to tetraethyl orthosilicate, and alcohol refers to ethanol；
Ammonia, refers to containing NH3The aqueous solution of mass percent about 18%；
First roasting source of the gas, refers specifically to oxygen and helium mix gas, and the volume ratio that wherein oxygen is accounted for is 4.9%.
Step 2, the first mixed liquid dipping；Concrete grammar is as follows：
Initial load sections catalyst described in step one is completely soaked in the first mixed liquor；The time is completely soaked for 24
h；After immersion is completed, the first unnecessary mixed liquor is filtered out, load typed iron catalyst granule is left.
Step 3, alkali catalyzed hydrolysiss；Concrete grammar is as follows：
Prepare the first container and second container；Unlimited second container, the quality for being put into ammonia are about initial load sections catalyst
25 times of quality；The load typed iron catalyst completed obtained by step 2 is put in the first container, and the first container is put into
Second container；Hermetic container will be formed on the lid lid of second container；After closeing the lid, 24 h are kept；Take out in the first container
Load typed iron catalyst.
Step 4, catalyst roasting；Concrete grammar is as follows：
Load typed iron catalyst obtained by step 3 is processed is exposed under the atmosphere formed by the first roasting source of the gas and is roasted
Burn；Roasting time is 6 h, and sintering temperature is 650oC。
Step 5, multiple circulate operation；Concrete grammar is as follows：
Using the load typed iron catalyst completed obtained by the step 4, " original negative described in alternative steps one " raw material preparation "
Carry sections catalyst " raw material, carry out new one cycle operation；The total degree that circulate operation is performed is 6 times.
In step 5, involved liquid composition in arbitrarily once new circulate operation, gas composition, sintering temperature,
The operating parameters such as roasting time, soak time are identical with the parameter of its front circulate operation.
Obtained product is referred to as " modification sections catalyst ".
The reaction system of modification sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor,
As shown in figure 1, wherein main reactor tube 1 is a cylindrical pipe, its internal diameter is 11 mm, and length is 60 cm；Wherein indifferent gas
Bromhidrosis source 6 is provided containing N2The gaseous mixture of gas 9.8%, He gas 90.2%；" modification sections catalyst " obtained in said process is loaded
Beds 12, section of the beds 12 full of main reactor tube 1 are formed in main reactor tube 1；The modification sections of filling
Gross mass m of catalystcat = 0.5 g。
The reaction condition control of ethane catalysis oxidation, concrete grammar are as follows：
Oxygen source 4, ethane source of the gas 5 and noble gas source 6 are opened, and is controlled by first flow controller 7, second flow
Device 8 and the 3rd flow controller 9 control the flow velocity of oxygen, ethane and noble gases respectively；The mass velocity F of control ethane
(C2H6) = 0.48 mcat*h-1, control the mass velocity F (O of oxygen2) for F (C2H6) 3.6 times, control noble gases matter
Amount flow rate F (Inert) is F (C2H6) 20 times；The temperature for controlling beds 12 is 600oC。
When the temperature of all of gas flow rate and beds 12 reaches setting value, the reaction bar of ethane catalysis oxidation
Part control is finished, and starts continuous production.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysissC2%
=100%, the yield of carbon dioxideY% = 70.5%。
Embodiment two,
This example is comparative example, it is therefore an objective to one of good effect of the checking present invention.Specific practice is：
Do not carry out the preparation of " modified iron catalyst "；
The reaction system of load typed iron catalyst catalysis ethane oxidation prepares：With " the modification sections catalyst second of embodiment 1
The reaction system of alkoxide prepares ", difference is that " modification sections catalyst " therein be substituted for " initial load sections is urged
Agent ", and be filled in the beds of ethane oxidation fixed-bed reactor；The initial load sections catalyst of filling
Gross mass mcat = 0.5 g。
The reaction condition control of ethane catalysis oxidation, with embodiment one.
When the temperature of all of gas flow rate and beds 12 reaches setting value, the reaction bar of ethane catalysis oxidation
Part control is finished, and starts continuous production.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysissC2%
=63.2%, the yield of carbon dioxideY% = 58.2%。
One, two result is it is found that use unmodified original negative using modification sections catalyst ratio in conjunction with the embodiments
Sections catalyst is carried, ethane can more completely be converted under the conditions of same process, and complete oxidation is produced in conversion process
Thing is more.That is, the former has the performance for preferably removing small molecule alkane.
Embodiment three,
Other with embodiment one, difference are：
For the preparation process of modification sections catalyst, in " the raw material preparation " of step one, the first mixed liquor, its concrete preparation side
Method is that the quality of latter of which is the former 0.41 times by alcohol and two class material mixing of positive esters of silicon acis；What wherein positive esters of silicon acis referred to
It is tetraethyl orthosilicate, alcohol refers to ethanol；In " the multiple circulate operation " of step 5, the total degree that circulate operation is performed is 9 times.
After continuous production starts, be calculated by online gas chromatographic analysiss the ethane of the present embodiment conversion ratio, two
The yield of carbonoxide is almost consistent in range of error.
Example IV,
Other with embodiment one, difference are：
For the preparation process of modification sections catalyst, in " the multiple circulate operation " of step 5, it is total secondary that circulate operation is performed
Number is 2 times.
For the reaction condition of ethane catalysis oxidation is controlled, the temperature for controlling beds 12 is 570oC。
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysissC2%
= 88.9%。
Embodiment five,
Other with embodiment one, difference are：
For the preparation process of modification sections catalyst, in " the multiple circulate operation " of step 5, it is total secondary that circulate operation is performed
Number is 5 times；Wherein, in for the 1-3 time circulate operation, involved liquid composition, gas in arbitrarily once new circulate operation
The operating parameters such as body composition, sintering temperature, roasting time, soak time are identical with the parameter of its front circulate operation；For
The 4-5 time circulation, with the operating parameter difference that the 1-3 time circulates be：
" the catalyst roasting " of step 4, sintering temperature is 400oC, during roasting, exposed atmosphere is air.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysissC2%
= 98.0%。
Embodiment six,
Other with embodiment one, difference are：
The reaction system of modification sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor, such as Fig. 1
Shown, wherein main reactor tube 1 is a cylindrical pipe, and its internal diameter is 18 mm, and length is 72 cm；By obtained " modification type
Iron catalyst " is filled in beds 12 are formed in main reactor tube 1, section of the beds 12 full of main reactor tube 1；Fill out
Gross mass m of the modification sections catalyst of dresscat = 2.0 g。
The reaction condition control of ethane catalysis oxidation, concrete grammar are as follows：
Mass velocity F (the C of control ethane2H6) = 0.12 mcat*h-1, control the mass velocity F (O of oxygen2) for F (C2H6)
4.0 times, control noble gases mass velocity F (Inert) be F (C2H6) 25 times；The temperature for controlling beds 12 is
570 oC。
When the temperature of all of gas flow rate and beds 12 reaches setting value, the reaction bar of ethane catalysis oxidation
Part control is finished, and starts continuous production.
After continuous production starts, the conversion ratio X of the ethane of the present embodiment is calculated by online gas chromatographic analysissC2%
= 100%。
Claims (8)
1. it is a kind of to use the method for modifying sections catalyst ethane oxidation, it is characterised in that including modification sections catalyst
Preparation, the reaction system for modifying sections catalyst ethane oxidation prepares, and the reaction condition control of ethane catalysis oxidation
Three parts of system；The preparation process for wherein modifying iron catalyst includes following step：
Step one, raw material prepare；Including following raw material：
Initial load sections catalyst, containing catalyst carrier and active metal component；The chemical composition of catalyst carrier is oxygen
Change aluminum；Active metal component is ferrum or iron oxides；In initial load sections catalyst, the load capacity of ferrum is 0.5 ~ 10
wt%；The specific surface area of initial load sections catalyst is more than 100 m2/g；Initial load sections catalyst be graininess, granule
Magnitude range is within 10 ~ 200 mesh；
First mixed liquor, its concrete compound method are by alcohol and two class material mixing of positive esters of silicon acis, before the quality of latter of which is
0.2 ~ 15 times of person；Wherein positive esters of silicon acis refer to methyl silicate, tetraethyl orthosilicate, one in positive silicic acid propyl ester three,
Or their arbitrary proportion mixture；Wherein alcohol refers in methanol, ethanol, 1- propanol, 2- propanol, or they
Arbitrary proportion mixture；Obtained mixed liquor is referred to as the first mixed liquor；
Ammonia, refers to containing NH3Aqueous solution of the mass percent more than 3%；
First roasting source of the gas, refers specifically to compressed air, oxygen, nitrogen, argon, helium, or above-mentioned these gases are any
Ratio gaseous mixture；
Step 2, the first mixed liquid dipping；
Step 3, alkali catalyzed hydrolysiss；
Step 4, catalyst roasting；
Step 5, multiple circulate operation.
2. it is according to claim 1 to use the method for modifying sections catalyst ethane oxidation, it is characterised in that modification
The step of iron catalyst preparation process two, concrete grammar is as follows：
Initial load sections catalyst described in step one is completely soaked in the first mixed liquor；The time is completely soaked for 20
min ~ 48 h；After immersion is completed, the first unnecessary mixed liquor is filtered out, load typed iron catalyst granule is left.
3. it is according to claim 1 to use the method for modifying sections catalyst ethane oxidation, it is characterised in that modification
The step of iron catalyst preparation process three, concrete grammar is as follows：
Prepare two containers, be referred to as the first container and second container；First container is an open container；Second container
For a hermetic container with cover, whole first container under air-tight state, can be held；Under second container opening-wide state, it is put into
A certain amount of ammonia, its quality are 5 ~ 1000 times of initial load sections catalyst quality；To complete negative obtained by step 2
Carry sections catalyst to be put in the first container, and the first container is put into into second container；Wherein ammonia and the first container are put into
The time sequencing of two containers is random order；Hermetic container will be formed on the lid lid of second container；After closeing the lid, keep 4 ~
48h；Take out the load typed iron catalyst in the first container.
4. it is according to claim 1 to use the method for modifying sections catalyst ethane oxidation, it is characterised in that modification
The step of iron catalyst preparation process four, concrete grammar is as follows：
Load typed iron catalyst obtained by step 3 is processed is exposed in atmosphere, or is exposed to the first roasting source of the gas
Roasting under the atmosphere for being formed；Roasting time is 30 min ~ 24 h, and sintering temperature is 200 ~ 750oC。
5. it is according to claim 1 to use the method for modifying sections catalyst ethane oxidation, it is characterised in that modification
The step of iron catalyst preparation process five, concrete grammar is as follows：
Using the load typed iron catalyst completed obtained by the step 4, " original negative described in alternative steps one " raw material preparation "
Carry sections catalyst " raw material, carry out new one cycle operation；Wherein step one is referred to step 4 per " one cycle operation "
Described all operationss；The total degree that circulate operation is performed is 1 ~ 15 time；
In step 5, involved liquid composition, gas composition, sintering temperature, roasting in arbitrarily once new circulate operation
The operating parameters such as time, soak time, can be identical with the parameter of its front circulate operation, it is also possible to different；Parameter is selected
Fall in above-mentioned steps one to the scope described by step 4；
After above-mentioned steps one to step 5, " the initial load sections catalyst " described in step one " raw material preparation " becomes
Become " modification sections catalyst ".
6. it is according to claim 1 to use the method for modifying sections catalyst ethane oxidation, it is characterised in that wherein
The reaction system of modification sections catalyst ethane oxidation prepares, using ethane oxidation fixed-bed reactor, including：It is main anti-
Ying Guan, main reactor tube have main reactor tube air inlet, main reactor tube gas outlet；Oxygen source, there is provided purity oxygen；Ethane source of the gas,
Pure ethane gas are provided；Noble gas source, there is provided N2The mixture of one or more gases in gas, He gas, Ar gas；Oxygen
Gas source of the gas, ethane source of the gas, the flow of noble gas source pass through first flow controller, second flow controller and the 3rd respectively
Flow controller is controlling；Oxygen source is after first flow controller, ethane source of the gas after second flow controller, it is lazy
Property gas source is merged into after the 3rd flow controller all the way, becomes the unstripped gas of ethane oxidation；Flow of feed gas is become owner of instead
Should pipe air inlet, from main reactor tube gas outlet flow out；Catalyst can be filled in beds are formed in main reactor tube；All streams
The gas of Jing beds is final all to flow out from main reactor tube gas outlet, forms product gas；
Above-mentioned " modification sections catalyst " is filled in beds are formed in main reactor tube, beds are full of primary response
The section of pipe；The modification sections catalyst gross mass of filling is designated as mcat。
7. it is according to claim 1 to use the method for modifying sections catalyst ethane oxidation, it is characterised in that wherein
The reaction condition control of ethane catalysis oxidation, concrete grammar are as follows：
Open oxygen source, ethane source of the gas and noble gas source, and by first flow controller, second flow controller and
3rd flow controller controls the flow velocity of oxygen, ethane and noble gases respectively；The mass velocity of ethane is designated as into F (C2H6), oxygen
The mass velocity of gas is designated as F (O2), the mass velocity of noble gases is designated as F (Inert)；Control F (C2H6) in 0.07 ~ 3 mcat*
h-1In the range of；Control F (O2) for F (C2H6) 2 ~ 8 times；Control F (Inert) is F (C2H6) 1 ~ 50 times；Control catalyst
The temperature of bed is 300 ~ 750oA desired value between C.
8. it is according to claim 1 to use the method for modifying sections catalyst ethane oxidation, it is characterised in that ethane
Conversion ratio more than 85%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533390A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Iron-based oxygen carrier with interlayer shell structure and capable of catalyzing direct combustion of coal, and preparation method for iron-based oxygen carrier |
| WO2013111015A1 (en) * | 2012-01-23 | 2013-08-01 | King Abdullah University Of Science And Technology | Hydrogen generation |
| CN103933898A (en) * | 2014-05-08 | 2014-07-23 | 中国石油大学(华东) | Device and method for preparing ethylene from ethane oxidative dehydrogenation |
| CN103949243A (en) * | 2014-05-05 | 2014-07-30 | 中国石油大学(华东) | Stabilizing treatment method of platinum particles of loading type platinum catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013111015A1 (en) * | 2012-01-23 | 2013-08-01 | King Abdullah University Of Science And Technology | Hydrogen generation |
| CN102533390A (en) * | 2012-02-16 | 2012-07-04 | 华北电力大学 | Iron-based oxygen carrier with interlayer shell structure and capable of catalyzing direct combustion of coal, and preparation method for iron-based oxygen carrier |
| CN103949243A (en) * | 2014-05-05 | 2014-07-30 | 中国石油大学(华东) | Stabilizing treatment method of platinum particles of loading type platinum catalyst |
| CN103933898A (en) * | 2014-05-08 | 2014-07-23 | 中国石油大学(华东) | Device and method for preparing ethylene from ethane oxidative dehydrogenation |
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